Production of vat dyestuffs



Patented Jan. 19, 1932 UNITED STATES PAT/EN T OFFICE MAX ALBERT KUNZ, OF MANNHEIM, AND KARL KOBERLE, OF LUDWIGSHAFEN-ON-THE- BHIN E, GERMANY, ASSIG-NORS TO GENERAL ANILINE N. Y., A CORPORATION OF DELAWARE WORKS, INC., OF NEW YORK,

j PRODUCTION OF VAT DYES'IUFFS N 0 Drawing. Original application filed June 16, 1927,'Seria1 No. 199,420, and in Germany.il'zinuary14g1927.

Divided and this application filed July 28, 1928.

The subject matter of the present application has been divided out from our copending application for the manufacture of vat dyestuffs, Ser. No. 199,420, filed June 16, 1927, and relates to the manufacture of vat dyestuffs which are considered to be halogenated ms-anthradianthrones.

We have found that valuable vat dyestuffs are produced when halogen is introduced into the dyestuffs which are considered to be ms-anthradianthrones corresponding to the general formula: 0

and which may be obtained according to our copending applications Ser. Nos. 296,086, 296,087 and 296,088.

The new dyestuffs are distinguished from the ms-anthradianthrones which are free from halogen by their deeper color, which mostly is substantially more reddish and by their excellent afinity. Moreover, these new products are of great interest not only as vat dyestufis, but also as intermediate products for the manufacture of other vat dyestufis.

The introduction of halogen may be effected in various ways. For example, halogen, or agents liberating the same, may be allowed to act on the dyestuffs in the presence or absence of catalysts. Suitable catalysts for this purpose, are for example, iodine, sulfur, metals and metallic salts. The reaction is preferably carried on in solvents or diluents.

The properties of the ha-logeniferous insanthradianthrones can be substantially improved by introducing several different halogens into the ms-anthradianthrones. This is effected by treating the said anthrone derivative with different halogens either concurrently or successively, for example with Serial No. 296,089.

the presence --of solvents-or diluents and in the presence or absence of halogen transferrers. ogens into the vIns-anthradianthrones may also becfiected by introducing into such halogen-ms-anthradianthrones which are still capable oftaking up more halogen, another halogen, which differs fromthat' already contained in the original substance, the said in troduction being carried out in the manner already described.

1? or purification the halogenated insan thradianthrones may be recrystallized from solvents of high boiling point, or may be treated, in paste form, with hypochlorite. They give violet solutions in concentrated sulfuric "acid .and furnish, with an alkaline hydrosulfite solution bluish-violet vats from which orange dyeingsareobtained on cotton.

The following examples will further explain the nature of-the invention which however isnot restricted to these examples. The parts a-reby weight.

EwampZe 1 10 parts of ms-anthradianthrone are suspended in 200 parts of trichlorbenzene, 0.5 part of iodine being added, and chlorine passed in at C. until the reaction product acquires an orange-red color, which will occur in about an hour. After cooling, the orange-red precipitate is filtered by suction. The resulting dichlor-ms-anthradianthrone dissolves to a violet solution in concentrated sulfuric acid. The vat solution is bluishviolet and the resulting dyeings are orange.

Example 2 10 parts of ms-anthradianthrone are dissolved in 250 to 800 parts of nitrobenzene, and after addition of 0.5 part of iron filings or powder are treated with about 15 parts of bromine, stirred in at C. Stirring is continued for about i hours at the same temperature, and the dyestufi is filtered by suction after cooling. According to analysis, it is a dibromine derivative. It gives a violet solution in concentrated sulfuric acid, and a The introduction of different halbluish-violet vat which furnishes orange dyeings on cotton.

Example 3 A suspension of 1 part of ms-anthradianthrone in 20 parts of phosphorous oxychloride is boiled for 1 to 2 hours with 10 parts of phosphorous pentachloridc, after which the reaction product is decomposed with water and filtered oil by suction. The resulting brown monochlor-ms-anthradianthrone may be purified with hypochlorite; it ives extremely fast orange dyeings on cotton irom a bluish-violet vat.

What we claim is:

1. As new articles of manufacture dichlorms-anthradianthrones dissolving to a violet solution in concentrated sulfuric acid and forming a bluish-violet vat.

2. The process of producing new vat dyestufis which comprises subjecting an Ins-anthradianthrone to the action of a halogenating agent.

3. The process of producing new vat dyestufis which comprises subjecting an ms-anthradianthrone to the action of a halogenating agent in a diluting medium.

4. The process of producing new vatdyestuffs which comprises subjecting an ms-anthradianthrone to the action of a halogenating agent in a diluting medium in the presence of a halogen-transferrer.

5. The process of producing dichlor-msanthradianthrone which comprises subjectin ms-anthradianthrone suspended in trichTorbenzene to the action of chlorine in the presence of iodine.

In testimony whereof, we aflix our signatures.

MAX ALBERT KUNZ. KARL KOBERLE. 

